Nanostructured Metal Electrodes for Wool Processing and Electroanalysis
Degree GrantorUniversity of Canterbury
Degree NameDoctor of Philosophy
The research presented in this thesis firstly concerns the use of electrochemical techniques to develop approaches to wool processing which have a lower impact on the environment than conventional chemical methods. Wool is a sulfur rich substrate and current methods used in wool processing often rely on sulfur-based reducing agents such as metabisulfite. However, due to increasing concern over the environmental impacts of metabisulfite, alternative methods are of interest. Electrochemical techniques have been applied to the process of wool setting in the presence of thiol setting agents. Wool disulfide bonds are reduced during this process and the thiol setting agent is converted to the disulfide. Efficient conversion of the disulfide back to the thiol setting agent would allow catalytic amounts of thiols to be used in wool setting. The electroreduction of cystine and 2-hydroxyethyl disulfide has been examined at a range of metal and carbon electrodes to find efficient methods of generating the corresponding thiols, cysteine and 2-mercaptoethanol respectively. Gold and silver were identified as the most efficient electrode materials. In industrial wool processing, the use of large-scale metal electrodes is expensive and therefore, high surface area gold and silver nanoparticle electrodes were fabricated by electrochemically depositing the metals onto low-cost carbon substrates. The most efficient electrochemical system for generating the thiol setting agent involved the electroreduction of cystine at the gold nanoparticle electrode and this system was used to successfully demonstrate that wool setting can be achieved using relatively low concentrations of cysteine. Further research was carried out to investigate methods for the controlled preparation of metal nanoparticle electrodes and their utility for detecting hydrogen peroxide was examined. A simple and versatile approach for the preparation of tethered gold nanoparticle assemblies was developed by exploiting electrostatic interactions between citrate-capped gold nanoparticles and amine tether layers attached to carbon surfaces. The nanoparticle assemblies were optimised for the detection of hydrogen peroxide by selecting the size and density of electrostatically assembled nanoparticles. The number of amine functionalities on the surface and the assembly conditions controlled the nanoparticle density. Nanostructured palladium electrodes fabricated using vapour deposition methods to immobilise palladium nanoparticles directly onto carbon substrates were also examined for the electroanalysis of hydrogen peroxide.